The present invention is directed to processes for the production of rigid polyurethane foams and reaction systems for use therein. More specifically, the present invention is directed to processes for the production of rigid polyurethane foam utilizing a specific polyisocyanate composition, an isocyanate-reactive composition and hydrofluorocarbon or hydrocarbon blowing agents.
Rigid polyurethane foams have many known uses, such as in building materials and thermal insulation. Such foams are known to have superior structural properties, outstanding initial and long term thermal insulation and good fire retardation properties.
Rigid polyurethane foams have conventionally been prepared by reacting appropriate polyisocyanate and isocyanate-reactive compositions in the presence of a suitable blowing agent. With regard to blowing agents, chlorofluorocarbons (CFC""s) such as CFC-11 (CCl3F) and CFC-12 (CCl2F2) have been-used most extensively as they have been shown to produce foams having good thermal insulation properties, low flammability and excellent dimensional stability. However, in spite of these advantages, CFC""s have fallen into disfavor, as they have been associated with the depletion of ozone in the earth""s atmosphere, as well as possible global warming potential. Accordingly, the use of CFC""s has been severely restricted.
Hydrochlorofluorocarbons (HCFC""s) such as HCFC 141b (CCl2FCH3) and HCFC22(CHClF2) have become a widely used interim solution. However, HCFC""s have also been shown to cause a similar depletion of ozone in the earth""s atmosphere and accordingly, their use has also come under scrutiny. In fact, the widespread production and use of HCFCs is scheduled to end shortly.
Therefore, there has existed a need to develop processes for the formation of rigid polyurethane foams which utilize blowing agents having a zero ozone depletion potential and which still provide foams having excellent thermal insulation properties and dimensional stability.
A class of materials which have been investigated as such blowing agents include various hydrocarbons such as n-pentane, n-butane and cyclopentane. The use of such materials is well-known and disclosed, e.g., in U.S. Pat. Nos. 5,096,933, 5,444,101, 5,182,309, 5,367,000 and 5,387,618. However, known methods for producing foams with such blowing agents and reaction systems used in such methods have not been found to produce rigid polyurethane foams having commercially attractive physical properties at densities which are sufficiently low to make their use feasible. In short, the properties associated with such hydrocarbon blown foams have generally been inferior to CFC and HCFC blown foams.
Attention has also turned to the use of hydrofluorocarbons (HFC""s) including 1,1,1,3,3-pentafluoropropane (HFC 245fa); 1,1,1,3,3-pentafluorobutane (HFC 365mfc); 1,1,1,2-tetrafluoroethane (HFC 134a); and 1,1-difluoroethane (HWC 152a). The use of such materials as blowing agents for rigid polyurethane foams is disclosed, e.g., in U.S. Pat. Nos. 5,496,866; 5,461,084; 4,997,706; 5,430,071; and 5,444,101. However, as with hydrocarbons, attempts to produce rigid foams with such materials have generally not resulted in foams having structural, thermal and thermal properties comparable to those attained using CFC-11 as the blowing agent.
The majority of attempts to solve this problem have centered around the blending of different hydrofluorocarbons, hydrocarbons or the blending of hydrocarbons with hydrofluorocarbons and/or other blowing agents. Such attempts have met with limited success.
Accordingly, there remains a need for a process for the production of rigid polyurethane foam which utilizes hydrofluorocarbon or hydrocarbon blowing agents and which provides foams having excellent physical properties.
This objective is obtained by the present invention which utilizes polymeric polyisocyanates of a specific composition in the process for the production of rigid polyurethane foam with hydrofluorocarbon or hydrocarbon blowing agents. The present invention provides foams having improved physical and thermal insulation properties.
The present invention is directed to a process for making rigid polyurethane foams comprising reacting:
(1) a polyphenylene polymethylene polyisocyanate composition;
(2) an isocyanate-reactive composition containing a plurality of isocyanate-reactive groups which are useful in the preparation of rigid polyurethane or urethane-modified polyisocyanate foams;
(3) a hydrofluorocarbon or hydrocarbon blowing agent;
(4) optionally, water or other carbon dioxide evolving compounds, and
xe2x80x83wherein said polyphenylene polymethylene polyisocyanate comprises
(a) a 15 to 42 percent by weight, based on 100% of the polyisocyanate component (1), of diphenylmethane diisocyanate;
(b) 3-ring oligomers of polyphenylene polymethylene polyisocyanate (henceforth referred as triisocyanate) in an amount such that the ratio of diisocyanate to triisocyanate is between about 0.2 to about 1.8; and
(c) the remainder being higher homologues of polyphenylene polymethylene polyisocyanate.
The present invention is further directed to reaction system useful for the preparation of rigid polyurethane foams comprising
(1) a polyphenylene polymethylene polyisocyanate composition;
(2) an isocyanate-reactive composition containing a plurality of isocyanate-reactive groups which are useful in the preparation of rigid polyurethane or urethane-modified polyisocyanate foams;
(3) a hydrofluorocarbon or hydrocarbon blowing agent;
(4) optionally, water or other carbon dioxide evolving compounds, and
xe2x80x83wherein said polyphenylene polymethylene polyisocyanate comprises:
(a) a 15 to 42 percent by weight, based on 100% of the polyisocyanate component (1), of diphenylmethane diisocyanate;
(b) 3-ring oligomers of polyphenylene polymethylene polyisocyanate (henceforth referred as triisocyanate) in an amount such that the ratio of diisocyanate to triisocyanate is between about 0.2 to about 1.8; and
(c) the remainder being higher homologues of polyphenylene polymethylene polyisocyanate.
The polyphenylene polymethylene polyisocyanates used in the present invention are those of Formula I. 
The 3-ring oligomers of component 1(b) are those represented by Formula I where n=1. The higher homologues of component 1(c) are those represented by Formula I where n greater than 1.
The polyphenylene polymethylene polyisocyanate composition (1) used in the present invention comprises about 15 to about 42 percent, preferably about 20 to about 40 percent and more preferably 24 to about 38 percent by weight, based upon 100 percent of the polyisocyanate component, of diphenylmethane diisocyanates. Diphenylmethane diisocyanate in the form of its 2,2xe2x80x2, 2,4xe2x80x2 and 4,4xe2x80x2 isomers and mixtures thereof may be used as in the present invention. Any variation of the 2,2xe2x80x2, 2,4xe2x80x2 and 4,4xe2x80x2 isomers may be utilized. 
The polyphenylene polymethylene polyisocyanate composition (1) further comprises the triisocyanate component in an amount such that the ratio of diisocyanate to triisocyanate is between 0.2 to 1.8 and preferably between about 0.33 to about 1.8. Thus, the actual triisocyanate content is determined based upon the amount of diphenylmethane diisocyanate in the polyphenylene polymethylene composition (1) utilizing the above-stated ratio. The amount is on a percent by weight basis based on 100 percent by weight of the total polyisocyanate composition.
For purposes of clarification, if the amount of diphenylmethane diisocyanate in a given polyphenylene polymethylene polyisocyanate composition is 30 percent and the ratio of diisocyanate to triisocyanate is 1.5, the amount of triisocyanate which must be incorporated into the polyphenylene polymethylene polyisocyanate composition would then be 20 percent by weight based upon 100 percent by weight of the total composition. As used herein, the term xe2x80x9ctriisocyanatexe2x80x9d means all isomers of 3-ring oligomers of polyphenylene polymethylene polyisocyanate (i.e., n=1 in Formula I) containing three phenyl, two methyl and three isocyanate groups. Seven possible isomers of triisocyanate are described in xe2x80x9cChemistry and Technology of Isocyanatesxe2x80x9d by Henri Ulrich, John Wiley and Sons Inc., p. 388 (1996).
The remainder of the polyphenylene polymethylene polyisocyanate composition comprises higher homologues of polyphenylene polymethylene polyisocyanate. The higher homologues include all of those which are higher than tri, i.e., tetraisocyanate, heptaisocyanate, hexaisocyanate, etc (i.e., n greater than 1 in Structure 1). Suitable higher homologues are described in xe2x80x9cThe Polyurethanes Bookxe2x80x9d, edited by George Woods, John Wiley and Sons Publisher (1987). The amount of higher homologues contained within the polyphenylene polymethylene polyisocyanate composition is generally about 10 to about 77 and preferably about 19 to about 69 percent, based on 100 percent by weight of the total composition.
The higher homologue component (c) may further comprise higher functionality isocyanates modified with various groups containing ester groups, urea groups, biuret groups, allophanate groups, carbodiimide groups, isocyanurate groups, uretdione groups and urethane groups. Such modified isocyanates and methods for the preparation are known in the art.
The polyphenylene polymethylene polyisocyanate composition (1) is used in an amount of about 35 to about 70 of the total reaction system.
The polyphenylene polymethylene polyisocyanate composition (1) may be prepared by methods known to those skilled in the art. Suitable methods are disclosed, e.g., in xe2x80x9cChemistry and Technology of Isocyanatesxe2x80x9d Ulrich, John Wiley and Sons Inc. (1996). In general, the polyphenylene polymethylene polyisocyanate compositions are prepared by the reaction of aniline with formaldehyde under acidic conditions to form amines. This is followed by phosgenation and thermal cleavage of the resulting material into a mixture of isocyanate homologues. The amount of diphenylmethane diisocyanate, triisocyanate and higher homologues in the composition can be manipulated by adjusting the aniline to formaldehyde ratio and/or the reaction conditions. For example, a higher aniline to formaldehyde ratio results in a polyphenylene polymethylene polyamine which contains higher amounts of the diphenylmethane diamine component and the triamine component and a correspondingly lower yield of the higher homologue component. Therefore, phosgenation and thermal cleavage of the resulting polyphenylene polymethylene polyamine yields a polyphenylene polymethylene polyisocyanate product which contains higher amounts of the diphenylmethane diisocyanate and the triisocyanate and lower amounts of the higher homologues of isocyanate. Moreover, the composition of the polyphenylene polymethylene polyisocyanate component which contains can also be controlled by partial fractionation to separate diphenylmethane diisocyanate along with a variety of isocyanate modified reaction routes.
The isocyanate-reactive compositions (2) useful in the present invention include any of those known to those skilled in the art to be useful for the preparation of rigid polyurethane foams. Examples of suitable isocyanate-reactive compositions having a plurality of isocyanate-reactive groups include polyether polyols, polyester polyols and mixtures thereof having average hydroxyl numbers of from about 20 to about 1000 and preferably about 50 to 700 KOH/g and hydroxyl functionalities of about 2 to about 8 and preferably about 2 to about 6. Other isocyanate-reactive materials which can be used in the present invention include hydrogen terminated polythioethers, polyamides, polyester amides, polycarbonates, polyacetals, polyolefins, polysiloxanes, and polymer polyols.
Suitable polyether polyols include reaction products of alkylene oxides, e.g., ethylene, oxide and/or propylene oxide, with initiators containing from 2 to 8 active hydrogen atoms per molecule. Suitable initiators include polyols, e.g., diethylene glycol glycerol, trimethylolpropane, triethanolamine, pentaerythritol, sorbitol, methyl glucoside, mannitol and sucrose; polyamines, e.g., ethylene diamine, toluene diamine, diaminodiphenylmethane and polymethylene polyphenylene polyamines; amino alcohols, e.g., ethanolamine and diethanolamine; and mixtures thereof. Preferred initiators include polyols and polyamines.
Suitable polyester polyols include those prepared by reacting a carboxylic acid and/or a derivative thereof or a polycarboxylic anhydride with a polyhydric alcohol. The polycarboxylic acids may be any of the known aliphatic, cycloaliphatic, aromatic, and/or heterocyclic polycarboxylic acids and may be substituted, (e.g., with halogen atoms) and/or unsaturated. Examples of suitable polycarboxylic acids and anhydrides include oxalic acid, malonic acid, glutaric acid, pimelic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimellitic acid anhydride, pyromellitic dianhydride, phthalic acid anhydride, tetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, endomethylene tetrahydrophthalic acid anhydride, glutaric acid anhydride acid, maleic acid, maleic acid anhydride, fumaric acid, and dimeric and trimeric fatty acids, such as those of oleic acid which may be in admixture with monomeric fatty acids. Simple esters of polycarboxylic acids may also be used such as terephthalic acid dimethylester, terephthalic acid bisglycol and extracts thereof. While the aromatic polyester polyols can be prepared from substantially pure reactant materials as listed above, more complex ingredients may be advantageously used, such as the side-streams, waste or scrap residues from; the manufacture of phthalic acid, phthalic anhydride, terephthalic acid, dimethyl terephthalate, polyethylene terephthalate, and the like.
The polyhydric alcohols suitable for the preparation of polyester polyols may be aliphatic, cycloaliphatic, aromatic, and/or heterocyclic. The polyhydric alcohols optionally may include substituents which are inert in the reaction, for example, chlorine and bromine substituents, and/or may be unsaturated. Suitable amino alcohols, such as monoethanolamine, diethanolamine or the like may also be used. Examples of suitable polyhydric alcohols include ethylene glycol, propylene glycol, polyoxyalkylene glycols (such as diethylene glycol, polyethylene glycol, dipropylene glycol and polypropylene glycol), glycerol and trimethylolpropane.
The isocyanate-reactive material is used in an amount of about 20% to about 70% and preferably about 30% to about 60% of the total reaction system.
The present process further comprises reacting polyphenylene polymethylene polyisocyanate composition (1) and isocyanate-reactive composition (2) with one or more hydrofluorocarbon or hydrocarbon blowing agents which are vaporizable under foam forming conditions. The hydrofluorocarbon blowing agents useful in the present invention include: 1,1,1,3,3-pentafluoropropane (C-245fa); 1,1,1,3,3-pentafluorobutane (HFC 365mfc); 1,1,1,4,4,4-heptafluorobutane (HFC 356mff); 1,1-difluoroethane (HFC 152a), 1,1,1,2-tetrafluoroethane (HFC 134a) and mixtures thereof. Preferred hydrofluorocarbons include 1,1,1,3,3-pentafluoropropane; 1,1,1,3,3-pentafluorobutane and 1,1,1,2-tetrafluoroethane. Suitable hydrocarbons include butane, isobutane, isopentane, n-pentane, cyclopentane, 1-pentene, n-hexane, iso-hexane, 1-hexane, n-heptane, isoheptane, and mixtures thereof. Preferably the hydrocarbon blowing agent is isopentane, n-pentane, cyclopentane and mixtures thereof. The most preferred hydrocarbon blowing agent for use in the present invention is a blend of isopentane to n-pentane in a ratio of 80:20 to 99:1 parts by weight.
The hydrofluorocarbon blowing agent should be used in an amount of about 2% to about 20% and preferably about 4 to about 15 percent of the entire reaction system.
The hydrocarbon blowing agent should be used in an amount of about 2% to about 20% and preferably about 4% to about 15% of the entire reaction system.
Other physical blowing agents may also be used in the present process in combination with the hydrocarbon blowing agents. Suitable blowing agents include 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,2-tetrafluorethane (BFC-134a), 1,1-difluoroethane (BFC-152a), difluoromethane (HFC-32), chlorodifluoromethane (HCFC-22), and 2-chloropropane. When used, these blowing agents may be mixed into the isocyanate-reactive component, the isocyanate component and/or as a separate stream to the reaction system.
Vaporizable non-hydrofluorocarbons, such as 2-chloropropane, isopentane, cyclopentane may also be used in the present process in combination with the hydrofluorocarbon blowing agents. When used, the blowing agents may be mixed into the isocyanate-reactive component, the isocyanate component and/or as a separate stream to the reaction system.
The present process may optionally further comprise reacting the polyphenylene polymethylene polyisocyanate, the isocyanate-reactive composition and the hydrofluorocarbon or hydrocarbon blowing agents in the presence of water in an amount of 0.1% to about 5% and preferably about 0.2% to about 4% of the total reaction system. Water reacts to generate carbon dioxide to act as an additional blowing agent. Other carbon dioxide, evolving compounds may further be used in place of or in addition to water. Such compounds include carboxylic acids and cyclic amines.
The reaction system may further comprise one or more auxiliary agents or additives as needed for one or more particular purposes. Suitable auxiliaries and additives include crosslinking agents, such as triethanolamine and glycerol; foam stabilizing agents or surfactants, such as siloxane-oxyalkylene copolymers and oxyethylene-oxyalkylene copolymers; catalysts, such as tertiary amines, (e.g., dimethylcyclohexylamine, pentamethyldiethylenetriamine, 2,4,6-tris(dimethylaminomethyl) phenol, and triethylenediamine), organometallic compounds (e.g., potassium octoate, potassium acetate, dibutyl tin dilaurate), quatemary ammonium salts (e.g., 2-hydroxypropyl trimethylammonium formate) and N-substituted triazines (N,Nxe2x80x2,Nxe2x80x3-dimethylaminopropylhexahydrotriazine); flame retardants such as organo-phosphorous compounds (such as organic phosphates, phosphites, phosphonate, polyphosphates, polyphosphites, polyphosphonate, ammonium polyphosphate (for example triethyl phosphate, diethy ethyl phosphonate, tris(2-chloropropyl)-phosphate) and halogenated compounds (such as tetrabromophthalate esters, chlorinated parrafins); viscosity reducers such as propylene carbonate and 1-methyl-2-pyrrolidinone; infra-red opacifiers such as carbon black, titanium dioxide and metal flakes; cell-size reducing compounds, such as inert, insoluble fluorinated compounds and perfluorinated compounds; reinforcing agents, such as glass fibers and ground up foam waste; mold release agents, such as zinc stearate; antioxidants, such as butylated hydroxy toluene; and pigments such as azo-/diazo dyestuff and phthalocyanines. The amount of such auxiliary materials or additives is generally between about 0.1 to about 20%, preferably between about 0.3 to about 15% and most preferably between about 0.5 to about 10%, by weight based on 100% of the total foam formulation.
In operating the process for making rigid foams according to this invention, the known one-shot, prepolymer or semi-prepolymer techniques may be used together with conventional mixing methods, such as impingement mixing. The rigid foam may be produced in the form of slabstock, mouldings, cavity filling, sprayed foam, frothed foam or laminates with other material such as paper, metal, plastics, or wood-board. See, e.g., Saunders and Frisch, Polyurethanes Chemistry and Technology, Part II, Interscience Publishers, New York (1962), and the references cited for various methods of polyurethane formation.
The present invention further encompasses rigid polyurethane foams produced by the processes disclosed above.